1. Field of the Invention
The present invention relates to polymers. More particularly, the invention pertains to novel and useful polymers comprising a carbonoxygen backbone having a dioxycarbon moiety with a plurality of organic groups pendant from the dioxycarbon. The polymers are represented by the following general formula: ##STR2## wherein R.sub.1 is a di, tri or tetravalent alkylene, alkenylene, alkyleneoxy, cycloalkylene, cycloalkylene substituted with an alkyl, alkoxy or alkenyl, cycloalkenylene, cycloalkenylene substituted with an alkyl, alkoxy or alkenyl, arylene, or a arylene substituted with an alkyl, alkoxy or alkenyl, R.sub.2 and R.sub.3 are alkyl, alkenyl, alkoxy, alkenyloxy, alkylene, alkenylene, alkyleneoxy, alkenyleneoxy, alkylenedioxy, alkenylenedioxy, aryloxy, aralkyleneoxy, aralkenyleneoxy, aralkylenedioxy, aralkenylenedioxy, oxa, or OR.sub.1 O with R.sub.1 defined as above; and wherein, (a) R.sub.1 is divalent when R.sub.2 and R.sub.3 are alkyl, alkenyl, alkoxy, or alkenyloxy, with at least one of R.sub.2 or R.sub.3 an alkoxy or alkenyloxy; (b) R.sub.1 is divalent when R.sub.2 and R.sub.3 are intramolecularly covalently bonded to each other and to the same dioxycarbon atom to form a heterocyclic ring or a heterocyclic ring substituted with an alkyl, alkoxy or alkenyl when R.sub.2 is an alkyleneoxy or alkenyleneoxy and R.sub.3 is an alkyleneoxy, alkenyleneoxy or alkylene; (c) R.sub.1 is divalent when R.sub.2 and R.sub.3 are intramolecularly covalently bonded to each other and to the same dioxy carbon atom to form a fused polycyclic ring or a fused polycyclic ring substituted with an alkyl, alkoxy or alkenyl when R.sub.2 is an oxa, alkyleneoxy or alkenyleneoxy and R.sub.3 is aryloxy, aralkyleneoxy, aralkenyleneoxy or aralkylene; (d) R.sub.1 is divalent when R.sub.2 or R.sub.3 is an OR.sub.1 O bridge between polymer backbones bonded through their dioxycarbon moieties, and the other R.sub.2 or R.sub.3 is an alkyl, alkenyl, alkyloxy, or alkenyloxy; (e) R.sub.1 is tri or tetravelent when R.sub.2 and R.sub.3 are covalently bonded to each other and to the same dioxycarbon atom to form a heterocyclic ring or a heterocyclic ring substituted with an alkyl, alkoxy or alkenyl when R.sub.2 is an alkyleneoxy or alkenyleneoxy and R.sub.3 is an alkyleneoxy, alkenyleneoxy or alkylene; (f) R.sub.1 is tri or tetravalent when R.sub.2 and R.sub.3 are covalently bonded to each other and to the same dioxy carbon atom to form a fused polycyclic ring or fused polycyclic ring substituted with an alkyl, alkoxy or alkenyl when R.sub.2 is an oxa, alkyleneoxy or alkenyleneoxy and R.sub.3 is aryloxy, aralkyleneoxy, aralkenyleneoxy or aralkylene.
The polymers provided by the invention include homopolymers, copolymers of the random and block types formed by reacting monomers or mixtures of preformed homopolymers and/or copolymers, branched polymers and cross-linked polymers. The invention also makes available to the art thermoplastic linear polymers when R.sub.1 is divalent, R.sub.2 and R.sub.3 are substituted with a noncross-linking group or are bonded intramolecularly; thermosetting cross-linked polymers when R.sub.1 is divalent and R.sub.2 or R.sub.3 is intermolecularly bonded between different polymeric backbones; and, thermosetting cross-linked polymers when R.sub.1 is tri or tetravalent and R.sub.2 and R.sub.3 are substituted with noncross-linking groups, or bonded intramolecularly.
2. Description of the Prior Art
The reaction of orthoesters with glycols leading to non-polymeric and other diverse products is known to the art in the references such as Ind. J. Appl. Chem., Vol. 28, No. 2, pages 53 to 58, 1965 wherein Mehrota, et al obtained monoethoxy-monoglycolate and triglycoxy-bisorthoformate by reacting orthoformate with hexamethylene glycol in molar ratios of one to one, and two to three to yield low molecular weight compounds. Similarly, Crank, et al in Aust. J. Chem., Vol. 17, pages 1392 to 1394, 1964, disclosed the reaction of triols with orthoesters including ethyl orthoformate with butane 1,2,4-triol, pentane-1,2,5-triol and pentane-1,3,5-triol to form monomeric bicyclic compounds. During the preparation of the bicyclic orthoesters by reacting ethyl orthoformate with triols, Crank, et al found that compounds produced from starting materials having a 1,2-diol structure also contained compounds having ethylene linkages. In a subsequent paper, Crank, et al Aust. J. Chem., Vol. 17, pages 1934 to 1938, 1964, developed this reaction into a synthetic procedure for the conversion of 1,2-diols into olefins. Later, DeWolfe in Carboxylic Ortho Acid Derivatives, 1970, published by Academic Press, Inc., New York, noted that carboxylic orthoesters are more reactive toward acid hydrolysis than almost any other class of compounds, and this high hydrolytic reactivity complicates their synthesis and storage. DeWolfe reported that the conversion of diols to cyclic orthoesters including alkoxydioxolane or alkoxydioxane, followed by acid hydrolysis, provides a method for monoacylating diols. More recently, Bailey reported in Polym. Prepr. Amer. Chem. Soc. Div. Polym. Chem., Vol. 13, No. 1, pages 281 to 286, 1972, that the polymerization of spiro orthoesters at ambient and elevated temperatures led to polyesters and polycarbonates of the structures [--CH.sub.2 CH.sub.2 CH.sub.2 COOCH.sub.2 CH.sub.2 O--].sub.n and [--OCH.sub.2 OCOOCH.sub.2 CH.sub.2 CH.sub.2 --].sub.n.